Research J ournal of Applied Sciences, Engineering and Technology 3(8): 701-706, 2011

ISSN: 2040-7467
Maxwell Scientific Organization, 2011
Received: March 19, 2011 Accepted: J uly 02, 2011 Published: August 30, 2011
701
Critical Processes Involved in Formulation of Water-in-Oil
Fuel Emulsions, Combustion Efficiency of the Emulsified Fuels
and Their Possible Environmental Impacts
A.N. Dibofori-Orji
Department of Chemistry, Rivers State , University of Education, P.M.B. 5047,
Rumuolumeni, Port Harcourt, Nigeria
Abstract: The aim of this study is to highlight some problems encountered during the formulation of water-in-
oil (w/o) emulsions of diesel fuel. The combustion efficiency of the resultant emulsions and some pollutant gas
emissions were determined. The paper also discussed possible environmental impacts of these emissions.
Internal Combustion Engines (ICE) find application in many modes of transportation including marine, land
and air transportation. Economic and environmental considerations have led to the quest for improved
combustion efficiency of the various fossil fuels used for these modes of transportation. The possibility of
combustion of emulsified fuels has been the centre of some research efforts in the search for improved
combustion efficiency. Diesel is mixed with water to form fuel-oil emulsions for combustion in some internal
combustion engines. Depending on certain factors, two possible types of fuel-oil emulsions can be obtained:
Oil in water and water in oil emulsions. Combustibility of the resulting emulsions was investigated. In this
study, neat diesel was emulsified using polyethylene glycol as the emulsifying agent to produce water in oil
emulsions. The water in oil emulsion was found to be combustible within certain limits of percentage content
of water and air/fuel ratios. Problems encountered in the attempts to burn the emulsions include the nature and
type of emulsifying agent, the method and means of mixing, as well as stability of the emulsions. This study
shows that the emulsion containing 5% water had the highest combustion efficiency. Combustion of fuels,
whether neat or emulsified, has some environmental impacts. Different noxious substances as exhaust products
of combustion when emitted into the atmosphere could be injurious to human health, plants and animals within
or close to the operating environments. In this study, the exhaust gases were analysed and their possible
environmental impacts were discussed. The emulsion containing 7.5% water produced the least percentage of
carbon monoxide (CO), a highly pollutant gas. Generally, emulsified fuels produce better combustion efficiency
and less negative environmental emissions than neat fuels.
Key words: Combustion rig, emulsifying agent, emulsions, fossil fuels
INTRODUCTION
Mans quest to travel faster, improve comfort,
eradicate diseases, improve and increase agricultural
production, alleviate poverty as well as increasing life
expectancy etc., has led to the execution of several
projects that in the short and long run are not
environmentally friendly (Orji-Dibofori, 2004). One of
such projects is the Internal Combustion Engines (ICE)
used for transportation and other engineering and
industrial services today (Edward and Nicholas, 1988).
ICE finds application in many modes of
transportation including marine, automobile and aviation
transportation. Transport accounts for nearly one-third of
the total global energy consumption, and contributes
about 25% of the world carbon dioxide (CO
2
) output, as
well as Chlorofloro-Carbons (CFCs), Methane (CH
4
) and
Nitrous Oxide (NO
x
) emissions (Boyle and Ardill, 1989).
In the European Union (EU), 26 percent of the total
anthropogenic CO
2
emissions come from transport. The
threat on global climatic changes has evolved into politics
of climate change (Riordan and J ager, 1995). The
political, moral and legal responses to climatic changes in
the midst of significant socio-economic policy shifts have
been critically analysed. Climate change has been put on
policy agenda of the EU and the United Nations (UN)
framework conventions and subsequent conference of
parties.
In the wake of the global awareness on climate
change, several efforts and technologies are emerging to
cut down on emission of green house gases as well as
sustaining world economy for the present and future
generations. Recently, bio-diesel and ethanol-petrol have
been formulated as alternative fuels for automobiles and
the marine industry (NNPC, 2007). Prior to this,
researches had been undertaken into combustion of
Res. J. Appl. Sci. Eng. Technol., 3(8): 701-706, 2011
702
H
O
O
H
emulsified fuels to reduce emission of pollutant gasses
(CO
2
, CO, NO
X
CH
3
, SO
x
etc.) into the environment.
The aim of this study is to highlight some problems
encountered in formulating water-in-oil (w/o) emulsions
of diesel fuel: the nature and type of emulsifying agent,
the method and means of mixing as well as the stability of
the w/o emulsions. The combustion efficiency and some
pollutant gas emissions analysed in the study are also
discussed. The study also discusses the environmental
impacts of burning neat fuel and fuel emulsions. The
benefits of using bio-fuels are also enumerated in this
study.
MATERIALS AND METHODS
Emulsion formation and stability: An emulsion is a
mixture of two liquids: the droplet phase referred to as the
dispersed or internal phase, and the surrounding liquid,
the continuous or external phase (Becher, 1965). Such
systems possess a minimal stability which may be
increased by the addition of various surface-active
materials or finely divided solids. These surfactants are
known as emulsifying agents or emulsifiers.
An emulsion consisting of water and oil can take two
forms: an oil-in-water emulsion designated (o/w), in
which the oil assumes the role of the internal phase; and
a water-in-oil emulsion (w/o) in which the oil is the
external phase. The form a particular emulsion system
assumes is determined by the chemical nature of the
emulsifying agent.
The stability of the emulsions especially with respect
to this study is of prime importance. The emulsion has to
pass through a length of tube from the mixing tank before
it is admitted into the combustion chamber. An unstable
emulsion would begin to separate before it enters the
combustion chamber.
Means of mixing: There are several types of
emulsification equipment available. These may include
ultrasonic devices, colloid mills, high pressure
homogenizers and mechanical mixers. In this study, the
Silverson Mechanical Mixer or emulsifier was used. It is
an adequate mixer that shears molecules of the liquid
phases and mixes then up. This mode of operation is
referred to as using brute force to break up the interface
between the liquid phases.
Choice of emulsifying agent: The real importance of the
emulsifier lies in the profound changes, especially of the
electric double layers near the interfaces.
The electric double layers, controls the stability of the
emulsion by hindering the coagulation of the particles.
The emulsifier effects dispersion because it is a molecule
with one water - loving (hydrophilic) tail and one oil-
loving (hydrophobic or lipophilic) tail. It therefore makes
Table 1: Hydrophile--Lipophile Balance (HLB) ranges and their
applications
Range Application
3-6 W/O emulsifiers
7-9 Wetting agents
8-12 O/W emulsifiers
12-15 Detergents
15-20 Solubilizers (or Hydrotrope)
Elshafie and Khalid (2008)
Fig. 1: Ethylene oxide
it possible for water and oil to become finely dispersed in
each other, creating a stable homogeneous, smooth
emulsion.
For this purpose, an emulsifier can be characterized
by a number specifying its hydrophile-lipophile Balance
(HLB), (Becher, 1965).
HLB for emulsifiers is still a subject of practical
interest. Bancrofts rules state that the type of emulsion
is dictated by the emulsifier that should be soluble in the
continuous phase (Elshafie and Khalid, 2008). HLB is
based on the concept that some molecules have
hydrophilic groups, other molecules have lipophilic
groups and some both. Weight of each group on a
molecule predicts what behavior the molecular structure
will exhibit. HLB values of emulsifying agents can be
determined experimentally through laborious
determination of emulsion stability. Griftins method for
non ionic surfactants is described as follows:
HLB =(20 M
EO
)/M
W
where M
EO
=Molecular Mass of the hydrophilic moiety
M
W
=Molecular Mass of the whole molecule
A HLB value of 0 corresponds to a completely
hydrophobic molecule and a value of 20 corresponds to a
molecule made up completely of hydrophilic components.
Surfactants with low HLB values typically around 4 are
more oil soluble and thus tend to make w/o emulsions,
while those with high HLB values are more hydrophilic
and tend to make o/w emulsions.
Table 1 gives the range of HLB numbers of emulsifiers
and their applications.
The emulsifier used in this study was polyethylene
glycol, a polymer of ethylene oxide, water and their
esters. A single unit of ethylene oxide has a molecular
weight of 2.06784 g/mol, the molecular formula: C
2
H
6
O
2
and a chemical structure as shown in Fig. 1.
Polyethylene emulsifiers vary in consistency from
liquid to solid, depending on the molecular weight
indicated by a number following the name. They are
Res. J. Appl. Sci. Eng. Technol., 3(8): 701-706, 2011
703
lipophiles used as surfactants, dispersing agents, solvents,
ointments and suppository bases, vehicles, and
tabletsexcipients. Some other specific groups are
lauromagrogols, nonoxynols, octoxynol and poloxamers.
Mode of adding the emulsifier: In emulsion formulation,
either of these methods could be used to achieve the
desired objective:
C Agent-in-water method: The emulsifier is dissolved
in the water phase and the oil added with suitable
agitation. This yields o/w emulsion. However, if a
w/o emulsion is desired, the oil addition must be
continued until phase inversion takes place.
C Agent-in-oil method: This is the reverse of (i). It
produces w/o emulsion directly.
C Nascent soap method: This is used for emulsions
stabilized by soaps.
C Alternate addition method: Water and oil are
added alternatively.
In this study, the agent-in-oil method was used to produce
the w/o emulsions used.
Time of agitation: Under normal conditions of
emulsification, the mean size of the particles decreases
very rapidly in the first few seconds and then gradually
attains the limiting value in 1-5 min. Thereafter, there
would not be any appreciable reduction in size. This was
the case during the formulation and stabilization of the
w/o emulsion in this study.
Intensity of agitation: The principal parameter which can
be varied to give different emulsions is the intensity of
agitation. More efficient agitation produces a better
emulsion.
The combustion RIG: The Hilton Continuous
Combustion Unit used in this study is designed for
research in combustion and fuel technology and for
demonstration of handling and operation of typical
furnace equipment. It is a constant pressure unit with a
medium pressure liquid-gas burner which fires into a
stainless steel water-cooled combustion chamber. The
combustion unit has provision for sight glasses and
tapping points.
Instruments and controls are incorporated to enable
the selection of a wide range of air/fuel ratios. The burner
and combustion chamber are sealed against air leakages
so that the air flow measured is the total amount used in
the combustion process. Exhaust gas analysis can be
carried out from any point within the combustion chamber
or zone. The equipment is designed to accommodate any
of the standard methods for gas analysis e.g., the Orsat
apparatus or Gas chromatograph. With accurate
measurement of the heat absorbed by the cooling water
and measurement of the exhaust gas temperature, a clear
picture of the effects of the major variables which
contribute towards the efficient use of liquid and gaseous
fuels is obtained.
Experimental procedure:
Emulsion preparation: Different percentages of water-
in-fuel (diesel) mixtures, adequately stabilized with 1%
polyethylene glycol were prepared (2.5, 5.0, 7.5 and
10.0%) in stainless steel containers. By means of the
Siliverson Mechanical Mixer, the mixtures were
respectively mixed and agitated thoroughly for a period of
5 minutes. It is worthy of note that the emulsifying agent
(1% polyethylene glycol) was dissolved in the diesel and
then the required percentage of water was added with
suitable agitation. The result is an emergence of different
w/o emulsions. To ascertain the strength or stability of the
emulsions, they were made to pass through a long tube
into the combustion chamber. A stable emulsion would
not coagulate or separate into the different component
parts. The study recorded some failed trial runs before
stable emulsions were obtained. Also, higher percentages
of w/o emulsions (i.e., >10% water) were prepared, but
attempt to burn them proved unsuccessful.
Combustion procedure: The combustion chamber was
ignited using propane gas. When the chamber was hot
enough and a steady flame created, a gradual change from
the gaseous fuel (propane) to liquid fuel (neat diesel or
emulsified diesel) was made. A steady mass flow rate of
the fuel was achieved and the corresponding air flow rate
to give the desired air/fuel ratio was calculated.
The combustion was allowed to proceed at the set
conditions until steady state conditions were attained.
The following readings were then taken: Exhaust
temperature (T
E
), cooling water outlet temperature (T
2
),
cooling water inlet temperature (T
1
), Air inlet temperature
(Ti
a
), and Fuel inlet temperature (Ti
f
)
Samples of the exhaust gases were taken for analysis
in the Orsat Apparatus and the air, fuel and cooling water
mass flow rates were also noted. The Stoichiometric
air/fuel ratio of plain diesel was calculated to be 14.7:1.
RESULTS AND DISCUSSION
Effect of the emulsifying agent: The choice of an
emulsifying agent is very important as it determines
whether the resulting emulsion will be of the o/w or the
w/o type. Emulsions for combustion processes must be of
the w/o type. If any o/w emulsion is formed, its
combustion will be very difficult, if not impossible, as
experienced in the early experiments of this investigation.
Res. J. Appl. Sci. Eng. Technol., 3(8): 701-706, 2011
704
4
5
4
0
3
5
3
0
2
5.00 2.50 0.0
W/o Fmulsion (%)
C
o
m
b
u
s
t
i
o
n

e
f
f
i
c
i
e
n
c
y

(
%
)
Fig. 2: Combustion efficiency v. W/O emulsion
In such an emulsion, the flame in the combustion chamber
cannot be sustained by the water surrounding the oil
droplets and will be rapidly extinguished. The emulsifying
agent used in this study is polyethylene glycol, a polymer
of ethylene oxide, water and their esters (Fig. 1).
Having obtained the appropriate agent, it is necessary
to determine experimentally the suitable quantity of it to
be added to the oil or water phase. In this study, the
former was the case. Too small a quantity will not provide
good emulsion stability, such that no sooner does the
mixture leave the mixing tank than it starts to separate
out. Such a situation will extinguish the flame when the
separated water portion enters the combustion chamber.
On the other hand, too large a quantity will cause
creaming of the resulting emulsion, that can hardly burn,
or would clog the pump blades, and thus impairing their
movements and action. Both effects of the quantity of the
emulsifying agents were experienced in the course of the
experiments for this investigation. After several trials, the
quantity of polytethylene glycol used was 1% by volume
of the total diesel (oil) content for each composition.
Combustion efficiency: There are many ways of defining
combustion efficiency based on various criteria. The
criterion for the choice of the definition given by the
equation:
= [iCpi/R(Ti - To) - iCpi/P(T
E
- To) - Cp
w
(T
2
- T
1
)]/
()h
R
)
F
where
h
R
=Enthalpy of reaction of fuel
To =Reference temperature (usually 298K)
Ti =Inlet temperature of reactants
T
1
, T
2
=Cooling water inlet and outlet temperatures,
respectively
=Mass flow rate of Combustion Unit cooling
water
=Combustion efficiency
Subscripts F, R, P, E, W designate fuel, reactants,
products, exhaust and cooling water respectively; is that
the principle of the Hilton Continuous Combustion Unit
is based on the exchange of enthalpies (Mayhew and
Rogers, 1978).
Using the equation, the combustion efficiencies for
the various emulsions were calculated and depicted in a
graphical form (Fig. 2). The curves show a consistent
increase in combustion efficiency compared with neat
diesel: However, the efficiency decreased with increasing
water content beyond 5% water content.
A lower combustion efficiency of neat fuel compared
to the w/o emulsions could be attributed to the physical
property of water. Water has a lower boiling point
(100C) than diesel fuel (200-400C). Thus when the
emulsion with water droplet dispersed in the oil
undergoes combustion; the water will be surrounded by a
diffusion flame from which heat is transferred into the
drop (J arvis, 1975).
The water will begin to vaporize before the bulk of
the oil. Super heated boiling or spontaneous nucleation
occurs explosively. This results in vaporization of the
water in part and impart of kinetic energy of the oil. The
overall effect is the breaking into smaller molecules or
atomization of the diesel oil resulting in higher
combustion efficiency compared with the neat fuel.
Pollutant gas emissions and their environmental
impacts: Four exhaust gases were measured and
quantified using the Orsat Apparatus. These are: CO
2
,
CO, O
2
, and N
2
. The 5% w/o emulsion yielded 13.0% CO
2
with <0% CO, while neat fuel (diesel) yielded 9.5% CO
2
and 0.2% CO. The higher CO
2
emission from 5%
emulsion could explain its greater combustion efficiency
(41.6%).
Table 2 gives a summary of percentages of the
exhaust gases emitted from neat fuel and the emulsions
with their respective combustion efficiencies.From this
study, emulsification of diesel (w/o) improved
combustion efficiency of the fuel, as shown in Fig. 2.
However, the amount of CO
2
emission from the
emulsions was high enough to be of environmental
concern. At high temperatures as are obtained in furnaces
and automobile engines, nitrogen combines with oxygen
to produce oxides of nitrogen (NO
X
). Ordinarily, at
normal atmospheric temperatures, nitrogen and oxygen in
air may not pose pollution problems. The volumes of
nitrogen (73.4-75.9%) and oxygen (8.2-15.8%) measured
at the exhaust are high enough to produce nitrous oxides
considering the high exhaust temperatures. CO emission
was not produced at an appreciable level. Obviously, the
formulation of emulsions from water and diesel could be
used to drive diesel engines, to cut down on the use of
neat fuel.
Res. J. Appl. Sci. Eng. Technol., 3(8): 701-706, 2011
705
Table 2: Percent gaseous emissions and combustion efficiencies of neat diesel, and w/o emulsions
W/O emulsion (%) CO
2
CO N
2
O
2
H
2
O Combustion efficiency
0% (Neat fuel) 9.5 0.2 74.6 12.0 3.9 27.0
2.5% 9.0 <0 75.2 12.1 3.7 39.4
5.0% 13.0 <0 73.4 8.2 5.4 41.6
7.5% 5.9 <0 75.9 15.8 2.4 39.9
10.0% 7.5 <0 74.8 14.6 3.1 35.0
CO
2
, NO
x
, CH
4
, and tropospheric (ground level)
Ozone (O
3
), with other potentially harmful chemicals
including carbon tetrachloride, are gases that are released
during human activities. They have an overall warming
effect on the global climate (Houghton et al., 1990).
These gases absorb infrared radiation in the range 7-12
:m, which is part of the window through which more
than 70% of the radiation emitted from the surface of the
earth escapes into space. They cause radiative forcing, a
measure of their ability to perturb the heat balance in a
simplified model of the Earth-atmosphere system.
According to Houghton et al. (1992), the contribution
made by the main green house gases to global warming
breaks down as follows: 72% due to CO
2
, 18% due to
CH
4
and 10% due to nitrous oxide.
Global awareness on world climate change is the current
topical issue. Humanity is faced with the challenge of
extremes of weather conditions, floods, heat waves,
draughts, etc. (Kemp, 1994).
Most recently in December, 2009, United Nations
(UN) climate change conference was held in Copenhagen.
For the first time, the shipping industry was singled out
for regulation (The Motorship, 2009).
It is certainly true that in terms of tons moved per
mile, ships have lower Carbon dioxide emissions (3%)
than other forms of bulk transport. But on the hand,
looking at total emissions, ships are responsible for high
levels of harmful substances such as Sulphur and
particulate matter via emission of smoke and soot.
Transport (i.e., shipping and aviation) has been excluded
from previous international protocols on emissions but the
general view is that this cannot last.
There is the need to formulate technologies that
would keep in check the emissions of pollutants into the
environment despite human activities. Improvements
should continue to be gained through automobile, ship
and aircraft designs and operational efficiency to
guarantee overall CO
2
emissions reduction.
In addition to such designs and operational
efficiency, fuels that are environmentally friendly should
be encouraged for use. Bio-diesels and ethanol-fuels
abound. Countries already using ethanol fuels include:
USA: E10, E85; Brazil: E10, E85; Argentina; E15;
Germany: E10; China: E10, and Thailand: E10. USA and
Brazil have already developed Flexible Fuel Vehicles
(FFV). These are Cars/Trucks that can run any blend of
unleaded gasoline with ethanol i.e. engines run on E10;
E85. Installed computer in the fuel system automatically
compensates for the varying amount of ethanol in the fuel
to assure optimum performance.
The benefits of using ethanol petrol (and bio-diesel)
may therefore include:
C Higher Octane rating
C Fuel burns cleaner and produces fewer harmful
emission
C Has lower auto ignition temperature
C Fuel is more environmentally friendly
C Reduces effect of global warming
C Fuel (E10) can be used in all cars
C Oxygenates can be produced from renewable sources
such as corn, sugar cane, cassava etc.
C The fuel is expectedly cheaper than conventional
fuels (NNPC, 2007)
CONCLUSION AND RECOMMENDATION
Preparation of stable emulsions presented a lot of
problems. It requires an emulsifying agent to produce
stable distillate fuel emulsions (diesel is a distillate fuel).
The choice of emulsifying agent is very important as a
w/o or o/w emulsion can be obtained, depending on the
chemical nature of the agent.
Successful combustion of fuels emulsified with water
can only be achieved if the emulsion is of the water-in-oil
(w/o) type. The limit on the percentage water content of
an emulsion for effective and controllable combustion
depends on the chemical nature of the emulsifying agent
(which must be of the w/o type or a lipophile) and the
mixing device employed.
Over the range of emulsions burnt during the
experiments, the emulsified fuels exhibited characteristic
higher combustion efficiency than the neat diesel fuel
under the same conditions. The maximum efficiency in
each case, was obtained with emulsions containing 5%
water.
Water-in-oil emulsions did not reduce the emission of
pollutant gases per se. In the past such formulation would
have been welcomed as shipping companies would have
embraced a fuel with higher combustion efficiency. But
with the present trend of global events, interest is directed
to operations that are rather environmentally friendly in
terms of low pollutant emissions.
Bio-fuels utilizing appropriate oxygenates are being
formulated especially in the developed World. The
developing World should also welcome this development.
The use of bio-fuels for the automobile, aviation and
Res. J. Appl. Sci. Eng. Technol., 3(8): 701-706, 2011
706
shipping industries is highly recommended. These Sectors
are known to introduce the greatest amounts of pollutants
into the atmosphere through exhaust emissions. The use
of bio-fuels, apart from being environmentally friendly
would create more job opportunities in the agro sector of
the economy. The net effect is a shift from over
dependence on fossil fuel as the primary source of energy
to renewable energy source (Oxygenates). The World
therefore should embark on projects that would sustain
the present and future generations.
REFERENCES
Becher, P., 1965. Emulsion Theory and Practice.
Reinhold Publishing Corporation.
Boyle, S. and J . Ardill, 1989. The Green House Effect.
London: Holder and Stoughton, pp: 298.
Edward, G. and H. Nicholas, 1988. The Earth Report:
Monitoring theBattle for Our Environment. Mitchell
Beazley International Ltd., London, pp: 240.
Elshafie, A.M.G. and S.K. Khalid, 2008. QSPR for HLB
of non ionic surfactant based polyoxyethylene group.
J . Dispersion Sci. Technol., 29: 940-947.
Houghton, J .T., G.J . J enkins and J .J . Ephraums, 1990.
Climate Change: The IPCC Scientific Assessment
Cambridge University Press, Cambridge, pp: 365.
Houghton, J .T., B.A. Callander and S.K. Varney, 1992.
Climate Change: The Supplementary Report to the
IPCC Scientific Assessment. Cambridge University
Press, Cambridge, pp: 200.
J arvis, T.J ., 1975. Bubble nucleation mechanisms of
liquid droplets superheated in other liquids. J . Colloid
Interface Sci., Vol. 50.
Kemp, D.D., 1994. Global Environmental Issues: A
Climatological Approach. 2nd Edn., London,
Routeledge, pp : 220.
Mayhew, Y.R. and G.F.C. Rogers, 1978.
Thermodynamics and Transport Properties of Fluids,
2nd Edn., Oxford Basil Blackwell, Country.
Riordan, O.T. and J . J ager, 1995. Politics of Climate
Change. Routeledge, London.
Orji-Dibofori, A. N., 2004. Level of awareness of the
general public on pollution caused by automobile
exhaust and its adverse effects on human health in
port harcourt metropolis. Technol. Edu. J ., 5(1): 149.
Research and Development Division, NNPC,. 2007.
Training Program (November) for PPMC Chemists
and Operators on E10 Fuel Handling. Port Harcourt,
Nigeria.
The Motorship, 2009. Nov. Edn., Retrieved from:
www.motorship.com.